Low-temperature CO2 capture technologies – Applications and potential

CO₂ capture by chemical or physical sorption and membrane separation have been the dominant fields of research within post- and pre-combustion CO₂ capture from power cycles and industrial processes. Except for oxy-combustion capture applications, limited attention has been given to low-temperature capture from flue gas and synthesis gas by phase separation. This paper gives an overview of common CO₂ capture conditions for a broad range of different power cycles and industrial processes. For a selected range of capture conditions, potential applications for low-temperature CO₂ capture have been evaluated with respect to energy consumption and CO₂ capture ratio. For all applications of low-temperature capture, specific power consumption and obtainable CO₂ capture ratio are sensitive to flue-gas or synthesis-gas feed CO₂ concentration. However, for certain applications such as synthesis gas from coal gasification, low-temperature capture shows promising potential and highly competitive energy figures compared to baseline technology.     

Decarbonised coal energy system advancement through CO2 utilisation and polygeneration

Development of clean coal technology is highly envisaged to mitigate the CO₂ emission level whilst meeting the rising global energy demands which require highly efficient and economically compelling technology. Integrated gasification combined cycle (IGCC) with carbon capture and storage (CCS) system is highly efficient and cleaner compared to the conventional coal-fired power plant. In this study, an alternative process scheme for IGCC system has been proposed, which encompasses the reuse of CO₂ from the flue gas of gas turbine into syngas generation, followed by methanol synthesis. The thermodynamic efficiency and economic potential are evaluated and compared for these two systems. The performances of the systems have been enhanced through systematic energy integration strategies. It has been found that the thermodynamic and economic feasibilities have attained significant improvement through the realisation of a suitably balanced polygeneration scheme. The economic potential can be enhanced from negative impact to 317?M€/y (3.6?€/GJ). The results have demonstrated promising prospects of employing CO₂ reuse technology into IGCC system, as an alternative to CCS system.     

气-液膜接触器结构优化及其传质性能研究

以海水作为吸收剂,采用模拟烟气,对气-液膜接触器进行传质性能评价试验,考察其工艺结构参数、气液介质流动速率及方式、气液压差、烟气SO2浓度等因素对传质系数、脱硫率及膜效用的影响.试验表明,在气相压力较低情况下,气液流速、气液压差对总气相传质系数影响明显,而烟气SO2浓度的影响可忽略不计.适当提高膜接触器的填充密度,增加膜吸收级数,采用错流模式的气液流动方式,均可改善烟气流场分布,增大有效传质面积,提高膜效用.与传统吸收塔相比,新型膜气体吸收装置的气液两相独立控制,可灵活应对烟气浓度变化对脱硫稳定性的影响,同时具有低气阻、耐污染、规模可线性放大等优点,工业化应用前景广阔.     

膜法海水吸收烟气中二氧化碳的试验研究

采用自制聚丙烯中空纤维膜接触器,以海水作为吸收剂,对模拟烟气中CO2进行吸收试验研究,主要考察烟气流量、CO2浓度、海水流量、海水pH值及膜填充率对CO2脱除率及膜接触器传质性能的影响.研究结果表明:(1)提高烟气流量或CO2浓度能提高膜接触器对CO2的处理量,导致脱碳率下降;(2)提高海水流量能明显提高脱碳率和传质速率;(3)提高海水pH可增大海水对CO2的吸收能力,直接决定了海水对CO2的吸收机制;(4)增大膜接触器填充率所对应的脱碳率并非最高,有效气液接触面积是影响脱碳率和过程传质的重要因素.     

膜接触器分离混合气中二氧化碳

以N-甲基二乙醇胺（MDEA）水溶液为吸收剂,采用疏水性聚丙烯中空纤维膜组件（HFPPM）作为膜接触器,研究了膜接触器分离CO2/N2混合气传质性能,主要考察了吸收剂浓度,液速,吸收温度,原料气浓度和气速等因素对CO2吸收性能的影响,比较了同一膜组件不同流程和不同膜组件及膜形态对分离效果的影响,并对膜组件运行的稳定性进行了初步考察,实验结果表明,采用MDEA溶液和HFPPM膜接触器分离CO2/N2混合气具有较快的传质速率和较高的分离效率．     

Exergy recuperative CO2 gas separation in pre-combustion capture

The integrated coal gasification combined cycle (IGCC) can achieve higher power generation efficiency than conventional pulverized coal combustion power plants. However, a CO₂ capture process prevents improving power generation efficiency of IGCC, because CO₂ separation from gas mixtures requires huge amounts of energy. Therefore, in this study, we analyzed the CO₂ separation process in the pre-combustion capture process using a process simulator (PRO/II) in the steady state, and proposed a new process using a modularity based on self-heat recuperation (SHR) technology to decrease energy consumption. Pre-combustion capture was applied in the IGCC plant, which involved coal gasification and CO-shift conversion with CO₂ capture. The results show that the energy consumption for the CO₂ separation process using SHR was decreased by two-thirds. This means that the power generation efficiency can be improved by SHR compared with conventional IGCC with a CO₂ capture process.     

Optimum synthesis of solvent-based post-combustion CO2 capture flowsheets through a generalized modeling framework

A generalized framework for the optimal design of post-combustion CO₂ capture processes based on a systemic and flexible equilibrium separation model that employs orthogonal collocation on finite elements techniques is proposed. Within this context, a column section of adaptive separation capability and functionality serves as the fundamental structural block for the identification of efficient separation schemes. Separation column sections in combination with heat transfer blocks, as well as stream splitters and mixers enable the generation and evaluation of alternative flowsheet configurations within a nonlinear optimization program. The main objectives for the flowsheet evaluation involve separation and thermal efficiency that eventually impact the economics of the overall process. Vapor–liquid equilibrium calculations are performed using statistical associating fluid theory for potentials of variable range (Mac Dowell et al., Ind Eng Chem Res 49:1883–1899, 2010). The proposed design framework is used for the optimal design of five alternative flowsheet configurations for the separation of CO₂ from a flue gas stream using a 30 % weight monoethanolamine aqueous solution. These flowsheets illustrate the various connection patterns between the process units and indicate suitable distribution of process-driving forces through which the overall efficiency can be drastically enhanced.     

Reforming natural gas for CO2 pre-combustion capture in combined cycle power plant

The aim of this study is to assess the conversion of a natural gas combined cycle power plant (NGCC) using an advanced gas turbine (GE9H) for CO₂ pre-combustion capture. The natural gas is reformed in an auto-thermal reformer (ATR) either with pure oxygen or with air. After water-shift conversion of CO into CO₂ and physical CO₂ recovery, the synthesis gas contains a high fraction of H₂. It is diluted with N₂ and steam to lower its low heating value (LHV) for NO _X emission control. Oxygen purity and reforming pressure have little impact on the performances. High-pressure reforming is preferred to reduce the process size. Air reforming results in a slightly higher efficiency but in a bigger process too. The CO₂ recovery rate has a big impact on the power plant efficiency since a lot of steam is required to lower the heating value (LHV) of the synthesis gas leaving the recovery process. Two values of LHV have been assessed. Steam consumption for natural gas reforming and synthesis gas dilution are the main consuming elements. An erratum to this article can be found at     

Removal of Nano-sized Particles Using Carbon Dioxide (CO2) Gas Cluster Cleaning without Pattern Damage

As pattern size of semiconductor device becomes less than 20 nm, the removal of particles smaller than 10 nm without pattern damages requires new physical dry cleaning technology. CO₂ gas cluster cleaning is an alternative dry cleaning process to meet these cleaning requirements. To demonstrate gas cluster cleaning performance, particle removal efficiency (PRE) and gate structure pattern damages were evaluated. When pressurized and low temperature CO₂ gas was passed through a convergence–divergence (C–D) nozzle, high energy CO₂ gas clusters were generated at high speed in a vacuum atmosphere. The cleaning force of the CO₂ gas cluster is related to the flow rate of the CO₂ gas. The optimum CO₂ gas flow rate for the particle removal without pattern damage was found to be 6 L/min (LPM). Removal efficiency for 50 nm silica particles was greater than 90%, and no pattern damage was observed on 60 nm poly-Si and a-Si gate line patterns. It was confirmed that the CO₂ gas cluster cleaning force could be controlled by the CO₂ gas flow rate supplied to nozzle.     

A maturity approach to estimate compressive strength development of CO2-cured concrete blocks

An alternative CO₂ curing method for precast concrete products has been proposed in order to achieve rapid strength development at early age, as well as to capture and store greenhouse gas (CO₂). In this paper, an experimental study for the development of a maturity approach is presented to estimate the strength development of carbonated concrete blocks. In order to promote the use of industrial flue gas containing CO₂, a flow-through CO₂ curing regime at ambient pressure and temperature was employed using different atmospheric conditions, such as various CO₂ concentrations, RH values and gas flow rates. The experimental results showed that the compressive strength or maturity of the carbonated concrete blocks was affected by two factors: accelerated cement hydration and carbonation extent. A high CO₂ concentration, a fast gas flow rate and a moderate relative humidity were essential for enhancing the maturity and the strength development. The developed model based on the maturity approach may accurately predict the strength development of the carbonated concrete blocks.     

Corrosion failures of AISI type 304 stainless steel in a fertiliser plant

A urea plant, operating on ammonia and carbon dioxide (CO₂) gases, had to be shutdown due to corrosion in the intercooler and aftercooler of its CO₂ gas cleaning circuit. Extensive general corrosion of AISI type 304 stainless steel parts, such as sealing strips, fins, demisters and the shell, of these two components which were in contact with the duplex stainless steel tubes, caused the shutdown of the fertiliser plant within 6 months. Investigations of the corrosion products by X-ray photoelectron spectroscopy (XPS) and X-ray diffraction (XRD) techniques showed the presence of carbon and ammonia based compounds, thus suggesting the role of ammonia and CO₂ gases, or the product of their reactions, in the corrosion of type 304 stainless steel. Electrochemical polarisation studies showed that duplex stainless steel possessed a more positive open circuit potential and a nobler critical pitting potential than type 304 stainless steel thus confirming that the corrosion of type 304 stainless steel was caused by the galvanic action with the duplex stainless steel heat transfer tubes. Hence, it was recommended that (i) the same material (type 304 stainless steel) be used for all parts of the intercooler and aftercooler to avoid galvanic corrosion, (ii) condense water carried over by CO₂ gas by cooling it to low temperatures immediately after it comes out from the scrubber, (iii) slight modification of the process to add up to 0.8% oxygen in the CO₂ gas before entry into the intercooler, which will help in retaining/formation of an effective passive film on type 304 stainless steel.     

Air stripping of ammonia in a water-sparged aerocyclone reactor

Air stripping of ammonia is a widely used process for the pretreatment of wastewater. Scaling and fouling on the packing surface in packed towers and a lower stripping efficiency are the two major problems in this process. New equipment that is suitable for the air stripping of wastewater with suspended solids has been developed. Air stripping of ammonia from water with Ca(OH)₂ was performed in the newly designed gas–liquid contactor, a water-sparged aerocyclone (WSA). WSA exhibited a higher air stripping efficiency and an excellent mass transfer performance, it also consumed less air compared with stripping tanks and packed towers. In addition, no scaling and fouling was observed in the inner structure of the WSA. During the stripping process, the stripping efficiency and mass transfer coefficient naturally increases with the liquid phase temperature and air flow rate. There is a critical value for the air flow rate over which stripping efficiency and the mass transfer coefficient increases rapidly. An efficient air stripping of ammonia should be conducted at a higher ambient temperature (>25 °C), and a higher air flow rate (>1.4 l/s).     

Life cycle assessment of membrane-based carbon capture and storage

Many investigations have conducted life cycle assessments (LCA) of the most commonly discussed routes of carbon capture and storage (CCS): post-combustion with amine wash separation; oxyfuel using cryogenic air separation and pre-combustion by integrated gasification combined cycle (IGCC) using physical separation. A research alliance developed corresponding separation systems using different types of membranes to allow a more energy efficient separation process: polyactive polymeric membranes for post-combustion, ceramic membranes for oxyfuel and metallic membranes for IGCC separation. By conducting an LCA, the study examines the actual greenhouse gas emissions and other environmental impacts of the new membrane separation technologies, together with concepts implementing the more common technologies. The reference systems represent today’s state-of-the-art supercritical coal fired power plant in Germany, together with a more advanced ultra-supercritical plant operating at 700 °C without CO₂ capture. The results demonstrate that among the three reference power plants the IGCC is the superior concept due to the highest efficiency. Regarding climate change, the IGCC power plants with CO₂ capture are still the best concepts. When other environmental impacts are considered, the capture technologies are inferior. The membrane concepts show the overall better results in comparison to the conventional capture technologies. The environmental impacts for membrane applications add a new range of findings to the field of CCS LCAs. Now the results for several different approaches can be compared directly for the first time.     

CO2‐Philic Separation Membrane: Deep Eutectic Solvent Filled Graphene Oxide Nanoslits

CO₂ capture and sequestration is an energy‐intensive industry to deal with the global greenhouse effect. Membrane separation is considered a cost‐effective method to mitigate the emission of CO₂. Though good separation performance and stability have been reported, supported ionic liquid membranes are still not widely applied for CO₂ separation due to the high cost. As a novel analogous solvent to ionic liquid, deep eutectic solvent retains the excellent merits of ionic liquid and is cheap with facile preparation. Herein, a highly CO₂‐philic separation membrane is constructed by nanoconfining choline chloride/ethylene glycol (ChCl/EG) deep eutectic solvent into graphene oxide nanoslits. Molecular dynamic simulation results indicate that the confinement makes a difference to the structure of the nanoconfined ChCl/EG liquid from their bulk, which remarkably facilitates CO₂ transport. By tuning the molar ratio of ChCl/EG and thickness of the membrane, the resultant membrane exhibits outstanding separation performance for CO₂ with excellent selectivity over other light gases, good long‐term durability, and thermal stability. This makes it a promising membrane for selective CO₂ separation.     

Membrane thinning for efficient CO2 capture

Abstract

Enhancing the fluxes in gas separation membranes is required for utilizing the membranes on a mass scale for CO₂ capture. Membrane thinning is one of the most promising approaches to achieve high fluxes. In addition, sophisticated molecular transport across membranes can boost gas separation performance. In this review, we attempt to summarize the current state of CO₂ separation membranes, especially from the viewpoint of thinning the selective layers and the membrane itself. The gas permeation behavior of membranes with ultimate thicknesses and their future directions are discussed.     

Effect of amine structure on CO2 capture by polymeric membranes

Abstract

Poly(amidoamine)s (PAMAMs) incorporated into a cross-linked poly(ethylene glycol) exhibited excellent CO₂ separation properties over H₂. However, the CO₂ permeability should be increased for practical applications. Monoethanolamine (MEA) used as a CO₂ determining agent in the current CO₂ capture technology at demonstration scale was readily immobilized in poly(vinyl alcohol) (PVA) matrix by solvent casting of aqueous mixture of PVA and the amine. The resulting polymeric membranes can be self-standing with the thickness above 3 μm and the amine fraction less than 80 wt%. The gas permeation properties were examined at 40 °C and under 80% relative humidity. The CO₂ separation performance increased with increase of the amine content in the polymeric membranes. When the amine fraction was 80 wt%, the CO₂ permeability coefficient of MEA containing membrane was 604 barrer with CO₂ selectivity of 58.5 over H₂, which was much higher than the PAMAM membrane (83.7 barrer and 51.8, respectively) under the same operation conditions. On the other hand, ethylamine (EA) was also incorporated into PVA matrix to form a thin membrane. However, the resulting polymeric membranes exhibited slight CO₂-selective gas permeation properties. The hydroxyl group of MEA was crucial for high CO₂ separation performance.     

Novel partial admission radial compressor for CO2 applications

A novel partial admission turbo compressor concept is proposed as an alternative to a conventional radial oil-free CO₂ compressor. The concept aims at the improvement of the overall performance through the reduction of the non-stage windage and cooling losses enabled by compression at significantly reduced shaft speeds. Transient CFD analysis gives fairly optimistic prediction of more than 80% of base stage efficiency at around 1.4 total pressure ratio. The study shows potential for efficiency improvement by optimization of the shape and number of blades. The conceptual compressor may be an interesting alternative for commercial CO₂ applications operating at close to critical pressures, provided that the deceleration of the gas in the diffuser is efficient.     

The Role of Interfacial Water in CO2 Electrolysis over Ni-N-C Catalyst in a Membrane Electrode Assembly Electrolyzer

CO₂ electrolysis is a promising route for achieving net-zero emission through decarbonization. To realize CO₂ electrolysis toward practical application, beyond catalyst structures, it is also critical to rationally manipulate catalyst microenvironments such as the water at the electrode/electrolyte interface. Here, the role of interfacial water in CO₂ electrolysis over Ni-N-C catalyst modified with different polymers is investigated. Benefiting from a hydrophilic electrode/electrolyte interface, the Ni-N-C catalyst modified with quaternary ammonia poly(N-methyl-piperidine-co-p-terphenyl) shows a Faradaic efficiency of 95% and a partial current density of 665 mA cm⁻² for CO production in an alkaline membrane electrode assembly electrolyzer. A scale-up demonstration using a 100 cm² electrolyzer achieves a CO production rate of 514 mL min⁻¹ at a current of 80 A. In-situ microscopy and spectroscopy measurements indicate that the hydrophilic interface significantly promotes the formation of the *COOH intermediate, rationalizing the high CO₂ electrolysis performance.     

Unobstructed Ultrathin Gas Transport Channels in Composite Membranes by Interfacial Self-Assembly

Ultrathin unobstructed gas transport channels through the membrane selective layer are constructed in mixed matrix membranes (MMMs) by using gravity-induced interface self-assembly of poly(vinylamine) and polymer-modified MIL-101(Cr). For CO₂/N₂ (15/85 by volume) mixed gas, the MMMs achieve a high CO₂ permeance of 823 gas permeation units and CO₂/N₂ selectivity of 242 at 0.5 MPa. Based on economic analyses, a two-stage membrane process can achieve gas separation and economic targets.     

2D Transition Metal Carbides (MXenes) for Carbon Capture

Global warming caused by burning of fossil fuels is indisputably one of mankind's greatest challenges in the 21st century. To reduce the ever‐increasing CO₂ emissions released into the atmosphere, dry solid adsorbents with large surface‐to‐volume ratio such as carbonaceous materials, zeolites, and metal–organic frameworks have emerged as promising material candidates for capturing CO₂. However, challenges remain because of limited CO₂/N₂ selectivity and long‐term stability. The effective adsorption of CO₂ gas (≈12 mol kg^?1) on individual sheets of 2D transition metal carbides (referred to as MXenes) is reported here. It is shown that exposure to N₂ gas results in no adsorption, consistent with first‐principles calculations. The adsorption efficiency combined with the CO₂/N₂ selectivity, together with a chemical and thermal stability, identifies the archetype Ti₃C₂ MXene as a new material for carbon capture (CC) applications.